Organic Chemistry II and Laboratory

Academic Year 2022/2023 - Teacher: GIUSEPPE TRUSSO SFRAZZETTO

Expected Learning Outcomes

The target of the course is to give a more inside knowledge of the Organic Chemistry respect to the first course, in particular relating to the chemical properties and reactivity. The main topics of the course will be carbohydrates, aminoacids and peptides, lipids, heterocycles. The course includes also 2 CFU of laboratory. During this activity, the target of the course will be the knowledge of the laboratory glass, and the ability to start a chemical reaction. Furthermore, the final target will be the use of some spectroscopic techniques, such as NMR, UV and IR, to establish the chemical structure of a unknown compound.

Course Structure

The course is divided into two parts: frontal lessons (in classroom) and laboratory activity. The frequency is mandatory.

Required Prerequisites

The acquisition of the objectives relating to the following disciplines is required: General and Inorganic Chemistry, Organic Chemistry I

Detailed Course Content

  • Enols and enolates: Keto-enol tautomerism - enolization catalyzed by acids and bases - stability of enols - acidity of hydrogen in a to carbonyl - anions enolate - lithiumenolates - halogenation of carbon a of aldehydes and ketones - reaction of haloform - halogenation of carbon to acids carboxylic - - Alkylation of carbon a - Alkylation and acylation of carbon a via an enamine intermediate - Aldol condensation: formation of ß-hydroxyaldehydes - Dehydration of an aldol condensation product - Cross aldol condensation - Mannich reaction - Claisen condensation: formation of ß-ketoesters - Other cross condensations - Intramolecular condensation and aldol addition reactions - Robinson's ringing - Decarboxylation of ß-ketoacids - Malonic synthesis - Acetacetic synthesis
  • Unsaturated alpha-beta carbonyls: Effects of conjugation - Reactions of conjugate additions - Alkylation of carbon b - Michael reaction - Nucleophilic attack on carbonyl or conjugate - "Hard" and "soft" nucleophiles - - reactions with ammonia and amines - reactions with alcohols and thiols - reactions with compounds organometallics and presence of Cu (I) salts - conjugate addition of enolates - conjugate addition followed by cyclization in the synthesis of rings
  • Heterocyclic compounds: Epoxides, aziridines, azirines and thiiranes, Classification of aromatic heterocycles - Heteroaromaticity - 5 and 6-membered heteroaromatic rings with a heteroatom: Furan, pyrrole, thiophene and pyridine. Synthesis by 1,3 and 1,4-dicarbonyl Heteroaromatic compounds with two or more heteroatoms - Benzocondensed heteroaromatic compounds - Aromatic electrophilic substitution, nucleophilic aromatic substitution, oxidation and reduction reactions - Pyridine N-oxide and electrophilic substitution.
  • Carbohydrates: Classification of carbohydrates - The D and L notation - Configuration of aldoses - Configuration of ketoses - Reactions of monosaccharides in basic solution - Reduction reactions of monosaccharides - Lengthening of the chain: the Kiliani-Fischer synthesis - Shortening of the chain: degradation of Wohl - Monosaccharides form cyclic hemiacetals - Formation of glycosides - The anomeric effect - Reducing and non-reducing sugars - Mutarotation - Disaccharides - Polysaccharides.

  • Amino acids, peptides and proteins: Nomenclature of amino acids - Configuration of amino acids - Acid-base properties of amino acids - The isoelectric point - Separation of amino acids - Methods of synthesis of amino acids - Resolution of a racemic mixture of amino acids - Peptide bonds and disulfide bonds - Peptide synthesis strategies - Peptide synthesis automated - Introduction to the structure of proteins - How to determine the primary structure of a polypeptide or a protein - Secondary structure of proteins - Tertiary structure of proteins - Quaternary structure of proteins.

  • pericyclic reactions: Conjugated dienes, molecular orbitals and symmetry, electrocyclic reactions, cycloadditions, sigmatropic transpositions, electrophilic additions, Dies-Alder, pericyclic reactions

  • Organometallic compounds and formation of new C-C bonds: C-C coupling reactions: irreversible covalent synthetic methodologies. Formation of new C-C bonds. Suzuki, Stille, Heck, Sonogashira, Negishi. Formation of new C = C bonds: Metathesis; Click Chemistry

  • Retrosynthesis: Basic principles of disconnections, Disconnection methodologies: synthesis of aromatic compounds, order of events, CX disconnections, chemoselectivity, synthesis of amines, protecting groups, CC disconnections (alcohols, aldehydes and ketones, carbonyl compounds), regioselectivity in ketone alkylations, disconnection of alkenes (elimination from alcohols, Wittig synthesis of dienes), use of acetylene.

  • Nucleic acids: Nucleosides and nucleotides, Other important nucleotides, DNA structure, Ribonucleic acids and RNA transcription, Genetic code.

    General principles of absorption spectroscopy. UV-VIS and IR spectroscopy. General principles and examples of applications to organic molecules.
    Gas chromatography. Essential factors inherent in the gas chromatographic technique. Chromatographic columns. High Pressure Liquid Chromatography (HPLC). General principles.
    NMR spectroscopy, Fourier transform NMR, Screen effect, multiplicity of signals, chemical shift, diamagnetic anisotropy, integration of signals, coupling constants. 13C NMR spectroscopy, two-dimensional NMR spectroscopy.

     Use of TLC for the identification of different organic substances present in the mixture: how do you proceed to choose the most suitable eluent mixture?
     Practical execution of reactions of:
     Electrophilic aromatic substitution: p-nitroaniline synthesis (protective groups).
     Multistep synthesis: preparation of a local anesthetic (benzocaine), nucleophilic acyl substitution.
    Isolation, purification and characterization of the products obtained in the single experiments by means of: melting point, UV-Vis, IR, 1H- and 13C-NMR.

Textbook Information

  • B. Botta, Chimica Organica, Ed. Edi.Ermes, Milano (ISBN 9788870513271);
  • P. Y. Bruice, Chimica Organica, Ed. EDISES, Napoli;
  • J. G. Smith, Chimica Organica, Ed. McGraw-Hill, Milano;
  • J. McMurry, Chimica Organica, Ed. PICCIN, Padova.
  • R.M. Silverstein, F.X. Webster, Identificazione Spettroscopica di Composti Organici, Ambrosiana.

Course Planning

 SubjectsText References
1Enoli ed enolatiBrown, appunti di lezione
2COMPOSTI CARBONILICI alfa-beta INSATURIBrown, appunti di lezione
3EterocicliciBrown, appunti di lezione
4CarboidratiBrown, appunti di lezione
5Amminoacidi e proteineBrown, appunti di lezione
6Reazioni PericiclicheBrown, appunti di lezione
7OrganometallicaBruice, appunti di lezione
8Acidi NucleiciBrown, appunti di lezione
9Metodi fisici in Chimica OrganicaR.M. Silverstein, F.X. Webster, Identificazione Spettroscopica di Composti Organici,

Learning Assessment

Learning Assessment Procedures

The exam will be taken orally. The exam topics will be strictly related to those developed during the lessons.

All the topics covered are considered essential for passing the exam. The laboratory experiences carried out will also be subject to application during the exam. For each laboratory experience, the student must submit a detailed report within 7 days of the exam date, which is also subject to evaluation during the exam.

Verification of learning can also be carried out electronically, should the conditions require it.